KR20120047308A - Process for the synthesis of fluorinated ethers of aromatic acids - Google Patents

Abstract

Fluorinated ethers of aromatic acids are produced from halogenated aromatic acids in a reaction mixture comprising a copper (I) or copper (II) source and a diketone ligand coordinated to copper. Fluorinated ethers of aromatic acids made using the methods described herein are applied to, for example, fibers, yarns, carpets, clothing, films, molded articles, paper and cardboard, stone, and tiles. Contamination, water resistance and oil resistance can be imparted. By incorporating fluorinated ethers of aromatic acids, or diesters thereof, into the polymer backbone, longer lasting fouling resistance, water resistance, and oil resistance, as well as improved flame retardancy can be achieved.

Description

PROCESS FOR THE SYNTHESIS OF FLUORINATED ETHERS OF AROMATIC ACIDS

This application claims 35 U.S.C. from U.S. Provisional Patent Application Ser. No. 61 / 239,194, filed Sep. 2, 2009, which is incorporated by reference in its entirety for all purposes. Claim priority under §119 (e) and claim the benefit of the provisional patent application.

The present invention relates to the production of fluorinated ethers of aromatic acids, or hydroxy aromatic acids, useful for a variety of purposes, such as use as surfactants, as intermediates, or as monomers for preparing polymers.

Fluorinated organic compounds have been used in a wide variety of applications, for example as surface treatments, for example as intermediates in the synthesis of pharmaceuticals, and as monomers in the synthesis of polymers with high value properties. In particular, as a compound or as a component of a polymer, fluorinated organic compounds are used to impart contamination resistance, water resistance and oil resistance and improved flame retardancy to materials, especially in the textile-related industries. In general, fluorinated compounds are applied by topical treatment, but their effects decrease over time due to material loss due to wear and washing.

Thus, there remains a need for providing polymeric materials with improved, longer lasting fouling and oil resistance.

The disclosure herein describes methods for the preparation of fluorinated ethers of fresh aromatic acids, fluorinated ethers of aromatic acids, methods of preparing products that can be converted from such fluorinated ethers, the use of such methods, and such methods. It includes the products obtained and obtainable by.

One embodiment of the method of the present invention is formula (I)

[Formula I]

Wherein Ar is a C ₆ to C ₂₀ monocyclic or polycyclic aromatic nucleus, n and m are each independently a non-zero value, n + m is 8 or less, and R _f is optionally one or more Fluorinated alkyl, alkaryl, aralkyl or aryl groups, including the ether linkage group —O—, provided that R _f is not attached to the ether oxygen of Formula (I) via a CF ₂ group or a CF ₂ CH ₂ CH ₂ group A process for producing a fluorinated ether of an aromatic acid, represented by the structure of

(a) Formula II:

≪ RTI ID = 0.0 &

Halogenated aromatic acids represented by the structure of wherein each X is independently Cl, Br or I, and Ar, n and m are as described above,

(i) a total of about n + m to about n + m + 1 equivalents of alcoholate R _f O ^- M ^{+ in a} polar aprotic solvent or in R _f OH as a solvent, per equivalent of halogenated aromatic acid M is Na or K);

(ii) a copper (I) or copper (II) source; And

(iii) Formula III:

[Formula III]

(Where A is

,

,

, 또는

이고,

,

,

, or

ego,

R ¹ and R ² are each independently substituted and unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl and tertiary alkyl groups; And substituted and unsubstituted C ₆ -C ₃₀ aryl and heteroaryl groups;

R ³ is H; Substituted and unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl and tertiary alkyl groups; Substituted and unsubstituted C ₆ -C ₃₀ aryl and heteroaryl groups; And halogen;

R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently H or a substituted or unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl or tertiary alkyl group;

p is contacted with a diketone ligand coordinated to copper, as represented by the structure of 0 or 1,

Forming a reaction mixture;

(b) heating the reaction mixture,

Formula III:

[Formula III]

Forming an m-basic salt of the product of step (a), as represented by the structure of;

(c) optionally, separating the m-basic salt of formula III from the reaction mixture in which the m-basic salt of formula III is formed; And

(d) contacting an m-basic salt of formula III with an acid to form a fluorinated ether of an aromatic acid therefrom.

Another embodiment of the present invention provides for the preparation of fluorinated ethers of aromatic acids described by the structure of formula (I), which are then used to prepare compounds, monomers, oligomers or polymers therefrom (including multistage reactions). By undergoing the reaction, a method of preparing a compound, monomer, oligomer or polymer is provided.

It has been found that by including fluorinated aromatic diesters in the polymer backbone, longer lasting fouling resistance, water resistance and oil resistance, as well as improved flame retardancy can be achieved.

The present disclosure provides the following general formula (I):

[Formula I]

Wherein Ar is a C ₆ to C ₂₀ monocyclic or polycyclic aromatic nucleus, n and m are each independently a non-zero value, n + m is 8 or less, and R _f is optionally one or more Fluorinated alkyl, alkaryl, aralkyl or aryl groups, including the ether linkage group —O—, provided that R _f is not attached to the ether oxygen of Formula (I) via a CF ₂ group or a CF ₂ CH ₂ CH ₂ group A process for producing a fluorinated ether of an aromatic acid, represented by the structure of

(a) Formula II:

≪ RTI ID = 0.0 &

Halogenated aromatic acids represented by the structure of wherein each X is independently Cl, Br or I, and Ar, n and m are as described above,

(i) a total of about n + m to about n + m + 1 equivalents of alcoholate R _f O ^- M ^{+ in a} polar aprotic solvent or in R _f OH as a solvent, per equivalent of halogenated aromatic acid M is Na or K);

(ii) a copper (I) or copper (II) source; And

(iii) Formula III:

[Formula III]

(Where A is

,

,

, 또는

이고,

,

,

, or

ego,

R ¹ and R ² are each independently substituted and unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl and tertiary alkyl groups; And substituted and unsubstituted C ₆ -C ₃₀ aryl and heteroaryl groups;

R ³ is H; Substituted and unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl and tertiary alkyl groups; Substituted and unsubstituted C ₆ -C ₃₀ aryl and heteroaryl groups; And halogen;

R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently H or a substituted or unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl or tertiary alkyl group;

p is contacted with a diketone ligand coordinated to copper, as represented by the structure of 0 or 1,

Forming a reaction mixture;

(b) heating the reaction mixture,

Formula IV:

[Formula IV]

Forming an m-basic salt of the product of step (a), as represented by the structure of;

(c) optionally, of formula IV

separating the m-basic salt of formula III from the reaction mixture in which the m-basic salt is formed; And

(d) contacting an m-basic salt of formula IV with an acid to form a fluorinated ether of an aromatic acid therefrom.

As used herein, the term "alkyl" denotes a monovalent group derived from an alkane by removing a hydrogen atom from any carbon atom: where -C _x H _{2x +1} (where x> 1). .

As used herein, the term "aryl" refers to a monovalent group where the free valence is relative to the carbon atom of the aromatic ring.

As used herein, the term "aralkyl" refers to an alkyl group having an aryl group. One such example is a benzyl group, ie radicals,

이다.

to be.

As used herein, the term "alkaryl" refers to an aryl group having an alkyl group. Some examples are 4-methylphenyl radicals,

,

,

Mesityl groups (ie 2,4,6-trimethylphenyl) and 2,6-diisopropylphenyl groups (ie (CH ₃ CHCH ₃ ) ₂ C ₆ H ₃ -radicals).

Examples of R _f include, without limitation, CF ₃ (CF ₂ ) _a (CH ₂ ) _b −, where a is an integer from 0 to 15 and b is 1, 3 or 4;

HCF ₂ (CF ₂ ) _c (CH ₂ ) _d −, where c is an integer from 0 to 15 and d is 1, 3, or 4;

CF ₃ CF ₂ CF ₂ OCFHCF ₂ (OCH ₂ CH ₂ ) _e -and

CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ (OCH ₂ CH ₂ ) _e −, where e is an integer from 1 to 12;

(CF ₃ ) ₂ CH-,

(CF ₃ CF ₂ CFH) (F) (CF ₃ ) C-,

(CF ₃ CF ₂ CFH) (F) (CF ₃ ) CCH _2- ,

(CF ₃ ) ₂ (H) C (CF ₃ CF ₂ ) (F) C-, and

(CF ₃ ) ₂ (H) C (CF ₃ CF ₂ ) (F) CCH ₂ —; And

Pentafluorophenyl is included.

In formulas (I), (II) and (IV), Ar is a C ₆ to C ₂₀ monocyclic or polycyclic aromatic nucleus; n and m are each independently a non-zero value and n + m is 8 or less; In formula (II), each X is independently Cl, Br or I.

The radical represented by is a C ₆ to C ₂₀ monocyclic or poly of an aromatic ring or formed by removing n + m hydrogens from different carbon atoms of the aromatic rings when the structure is polycyclic Cyclic aromatic nucleus. The radical “Ar” may be substituted or unsubstituted; If unsubstituted, only carbon and hydrogen are included.

One example of a suitable Ar group is phenylene, as shown below, where n = m = 1.

Suitable Ar groups are shown below, where n = m = 2.

"M-basic salt" is a salt formed from an acid comprising m acid groups with substitutable hydrogen atoms in each molecule, as the term is used herein.

Various halogenated aromatic acids, which are used as starting materials in the process of the invention, are commercially available. For example, 2-bromobenzoic acid is available from Aldrich Chemical Company (Milwaukee, WI). However, 2-bromobenzoic acid can be synthesized by oxidation of bromomethylbenzene, as described in Sasson et al, Journal of Organic Chemistry (1986), 51 (15), 2880-2883. Other halogenated aromatic acids that may be used include, without limitation, 2,5-dibromobenzoic acid, 2-bromo-5-nitrobenzoic acid, 2-bromo-5-methylbenzoic acid, 2-chlorobenzoic acid, 2,5-dichloro Benzoic acid, 2-chloro-3,5-dinitrobenzoic acid, 2-chloro-5-methylbenzoic acid, 2-bromo-5-methoxybenzoic acid, 5-bromo-2-chlorobenzoic acid, 2,3-dichloro Benzoic acid, 2-chloro-4-nitrobenzoic acid, 2,5-dichloroterephthalic acid, 2-chloro-5-nitrobenzoic acid, 2,5-dibromoterephthalic acid, and 2,5-dichloroterephthalic acid, all of which include Is available for purchase. Preferably, the halogenated aromatic acid is 2,5-dibromoterephthalic acid or 2,5-dichloroterephthalic acid.

Other halogenated aromatic acids useful as starting materials in the process of the invention include those shown in the left column of the table below, where X is Cl, Br or I, and the corresponding aromatics produced therefrom by the process of the invention. The ether of acid is shown in the right column:

In step (a), the halogenated aromatic acid is alcoholate R _f O ^- M ^{+ in a} polar aprotic solvent or in R _f OH as solvent, wherein R _f is as defined above and M is Na or K being); Copper (I) or copper (II) sources; And a ligand that coordinates to copper, the ligand comprising a Schiff base.

The alcohol may be R _f OH, which is preferred, or the alcohol may be an alcohol that is not more acidic than R _f OH. Examples of suitable alcohols include, without limitation, methanol, ethanol, i-propanol, i-butanol, and phenol, provided that the alcohol is not more acidic than R _f OH.

The solvent may also be a polar protic or polar aprotic solvent, or a mixture of protic or polar aprotic solvents. As used herein, a polar solvent is a solvent whose constituent molecule exhibits a nonzero dipole moment. As used herein, a polar protic solvent is a polar solvent whose constituent molecules comprise O-H or N-H bonds. As used herein, polar aprotic solvents are polar solvents whose constituent molecules do not comprise O-H or N-H bonds. Non-limiting examples of polar solvents other than alcohols suitable for use in the present invention include tetrahydrofuran, N-methylpyrrolidone, dimethylformamide, and dimethylacetamide.

In step (a), the halogenated aromatic acid is preferably contacted with a total of about n + m to n + m + 1 equivalents of alcoholate RO ^- M ⁺ per equivalent of halogenated aromatic acid. m to m + 1 equivalents are used to form the m-basic salt and n to n + 1 equivalents are used for the substitution reaction. It is preferable that the total amount of alcoholate does not exceed m + n + 1. In order to avoid the reduction reaction, it is also preferred that the total amount of alcoholate is at least m + n. As used in this context, one "equivalent" is the number of moles of alcoholate RO ^- M ⁺ that react with one mole of hydrogen ions; In the case of acids, one equivalent is the number of moles of acid that supplies one mole of hydrogen ions.

As mentioned above, in step (a), the halogenated aromatic acid is also contacted with a copper (I) or (II) source in the presence of a diketone ligand that coordinates to copper. The copper source and the ligand may be added sequentially to the reaction mixture or may be added together in combination separately (eg in a solution of water or acetonitrile).

The copper source is a Cu (I) salt, a Cu (II) salt, or a mixture thereof. Examples include, without limitation, CuCl, CuBr, CuI, Cu ₂ SO ₄ , CuNO ₃ , CuCl ₂ , CuBr ₂ , CuI ₂ , CuSO ₄ , and Cu (NO ₃ ) ₂ . The choice of copper source can be made in terms of the identity of the halogenated aromatic acid used. For example, when the halogenated aromatic acid as a starting material is bromobenzoic acid, CuCl, CuBr, CuI, Cu ₂ SO ₄ , CuNO ₃ , CuCl ₂ , CuBr ₂ , CuI ₂ , CuSO ₄ , and Cu (NO ₃ ) ₂ Will be included among the useful choices. If the starting halogenated aromatic acid is chlorobenzoic acid, CuBr, CuI, CuBr ₂ and CuI ₂ will be included among the useful choices. Optionally, prior to step (a), the measured amount (about 0.25 mol O ₂ per 1 mol CuI) can be added to dissolve CuI in the diamine / alcohol solution. CuBr and CuBr ₂ are generally preferred choices for most systems. The amount of copper used is typically about 0.1 to about 5 mol%, based on the moles of halogenated aromatic acid.

The ligand may be a diketone as represented by the structure of formula III:

[Formula III]

(Where A is

,

,

, 또는

이고,

,

,

, or

ego,

R ¹ and R ² are each independently substituted and unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl and tertiary alkyl groups; And substituted and unsubstituted C ₆ -C ₃₀ aryl and heteroaryl groups;

R ³ is H; Substituted and unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl and tertiary alkyl groups; Substituted and unsubstituted C ₆ -C ₃₀ aryl and heteroaryl groups; And halogen;

R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently H or a substituted or unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl or tertiary alkyl group; p is 0 or 1).

When used in connection with an alkyl or aryl group of a diketone as described above, the term "unsubstituted" means that the alkyl or aryl group does not contain atoms other than carbon and hydrogen. However, in substituted alkyl or aryl groups, as long as the resulting structure does not comprise a -OO- or -SS- moiety, and as long as the carbon atom is not bonded to more than one heteroatom, or in any one or more chains One or more O or S atoms may be optionally substituted in place of a carbon atom in the ring. In a preferred embodiment, R ³ is H.

In one embodiment, a suitable diketone for use in the present invention as a ligand is 2,2 ', 6,6'-tetramethylheptanedionone-3,5 (formula V):

[Formula V]

Other diketones suitable for use in the present invention as ligands include, without limitation, 2,4-pentanedione and 2,3-pentanedione.

Ligands suitable for use in the present invention may be selected as any one or more or all of the members of the entire population of ligands described by the above names or structures.

Various copper sources and ligands suitable for use in the present invention may be prepared by methods known in the art, or may be from Alfa Aesar (Ward Hill, Mass.), City Chemical. (West Haven, Connecticut), Fisher Scientific (Fairlon, NJ), Sigma-Aldrich (St. Louis, MO) or Stanford Materials ( Such as Aliso Viejo, California, USA.

In various embodiments, the ligand can be provided in an amount of about 1 to about 8, preferably about 1 to about 2 molar equivalents, of ligand per mole of copper. In such and other embodiments, the ratio of molar equivalents of ligand to molar equivalents of halogenated aromatic acid may be about 0.1 or less. As used herein, the term "molar equivalent" refers to the number of moles of ligand that interact with 1 mole of copper.

In step (b), the reaction mixture is heated to form an m-basic salt represented by the structure of formula IV:

[Formula IV]

The reaction temperature for steps (a) and (b) is preferably about 40 to about 120 ° C., more preferably about 50 to about 90 ° C. Typically, the time required for step (a) is from about 0.1 to about 1 hour. The time required for step (b) is typically about 1 to about 100 hours. Optimal times and temperatures may vary depending on the particular material. Preferably oxygen may be excluded during the reaction. The solution is typically allowed to cool before the optional step (c) and before the acidification is carried out in step (d).

The m-basic salt of the ether of aromatic acid is then contacted with the acid in step (d) to convert to the hydroxy aromatic acid product. Any acid of sufficient strength to protonate the m-basic salt is suitable. Examples include, without limitation, hydrochloric acid, sulfuric acid, and phosphoric acid.

In one embodiment, the copper (I) or copper (II) source is CuBr, CuBr ₂ And mixtures thereof; The ligand is selected from the group consisting of N, N'-dimethyl-2,3-diiminobutane and N, N'-di (trifluoromethylbenzene) -2,3-diiminoethane; The copper (I) or copper (II) source is combined with 2 molar equivalents of ligand.

Fluorinated ethers of aromatic acids prepared using the methods described herein include fibers, yarns, carpets, clothing, films, molded articles, paper and cardboard, stones, and to impart fouling, water and oil resistance. It can be made of tiles. By incorporating fluorinated ethers of aromatic acids, or diesters thereof, into the polymer backbone, longer lasting fouling resistance, water resistance, and oil resistance, as well as improved flame retardancy can be achieved.

The process described above also allows for the efficient and efficient synthesis of products prepared from fluorinated ethers of the resulting aromatic acids, such as compounds, monomers, or oligomers or polymers thereof. Such resulting materials include ester functional groups, ether functional groups, amide functional groups, imide functional groups, imidazole functional groups, thiazole functional groups, oxazole functional groups, carbonate functional groups, acrylate functional groups, epoxide functional groups, urethane functional groups, acetal functional groups, or It may have one or more of the anhydride functional groups.

Compounds of formula (I) may be isolated and recovered as described above, if desired. The compound of formula (I) may also be subjected to additional steps for converting the compound of formula (I) to another compound (eg, a monomer), or another product such as an oligomer or polymer, with or without recovery from the reaction mixture. Thus another embodiment of the process of the invention provides a process for converting a compound of formula (I) to another compound or to an oligomer or polymer via one or more reactions. Compounds of formula (I) are prepared by methods as described above and then, for example, oligomers or polymers therefrom, such as those having ester functional groups or amide functional groups, or pyridobisimidazole-2,6- The polymerization reaction to prepare a diyl (2,5-dihydroxy-p-phenylene) polymer can be carried out.

Compounds of formula (I), or diesters thereof, in particular dimethyl esters thereof, prepared by the methods disclosed herein are used in condensation polymerization, for example, without limitation, polyesters, polyamides, polyimides, and polybenziimi It is possible to produce fluorinated condensation polymers comprising doazoles. Representative reactions involving materials of the present invention, or derivatives of such materials, such as diesters, are described, for example, in US Pat. No. 3,047,536, which is incorporated in its entirety as part of the present invention for all purposes. According to the present invention, which comprises preparing a polyester from at least one compound of formula I and either diethylene glycol or triethylene glycol in the presence of 0.1% Zn ₃ (BO ₃ ) ₂ in 1-methylnaphthalene under nitrogen. Similarly, fluorinated ethers of aromatic acids are dibasic acids for preparing thermostabilized fluorinated polyesters according to the methods taught in US Pat. No. 3,227,680, which is incorporated by reference in its entirety for all purposes. And copolymerization with glycols, wherein representative conditions form the prepolymer in the presence of titanium tetraisopropoxide in butanol at 200-250 ° C. and then at 280 ° C. at a pressure of 10.67 Pa (0.08 mm Hg). Polymerizing.

Other diols useful for preparing polyesters from compounds of formula (I) are those derived from fermentation methods, and thus other embodiments of the present invention are methods for preparing oligomers or polymers from compounds of formula (I), from such fermentation methods. The method further includes the step of providing a diol.

For example, in a process in which polymerization takes place in solution in an organic compound that is liquid under reaction conditions, is a solvent for both the compound of formula (I) and diamine, and has a swelling or partial salvation action for the polymeric product, Compounds of formula (I) can be converted to polyamide oligomers or polymers by reaction with diamines. The reaction can be carried out at a moderate temperature, for example below 100 ° C., preferably in the presence of an acid acceptor which is also soluble in the chosen solvent. Suitable solvents include methyl ethyl ketone, acetonitrile, N, N-dimethylacetamide, dimethyl formamide-containing 5% lithium chloride-and N-methyl pyrrolidone-quaternary ammonium chloride- Such as methyl tri-n-butyl ammonium chloride or methyl-tri-n-propyl ammonium chloride. The combination of reactant components results in the generation of significant heat, and stirring also produces thermal energy. For this reason, solvent systems and other materials are always cooled during the process when cooling is required to maintain the desired temperature. Similar methods to those described above are described in US Pat. No. 3,554,966; US Patent No. 4,737,571; And Canadian Patent 2,355,316.

For example, in a process in which a solution of diamine in a solvent may be contacted with a solution of a compound of formula I in a second solvent that is incompatible with the first solvent in the presence of an acid acceptor to cause polymerization at the interface of the two phases, The compounds of I can also be converted into polyamide oligomers or polymers by reaction with diamines. Diamines can be dissolved or dispersed, for example, in water containing a base, where the base is used in an amount sufficient to neutralize the acid produced during the polymerization. Sodium hydroxide can be used as the acid acceptor. Preferred solvents for diacids (halides) are tetrachloroethylene, methylenechloride, naphtha and chloroform. The solvent for the compound of formula (I) should be relative non-solvent to the amide reaction product and relatively immiscible in the amine solvent. Preferred thresholds for immiscibility are as follows: The organic solvent should be soluble no greater than between 0.01% and 1.0% by weight in the amine solvent. Diamine, base, and water are added together and stirred vigorously. The high shear action of the stirrer is important. A solution of acid chloride is added to the aqueous slurry. The contact is generally performed at 0 ° C. to 60 ° C., for example for about 1 second to 10 minutes, and preferably at room temperature for 5 seconds to 5 minutes. The polymerization takes place rapidly. Similar methods to those described above are disclosed in US Pat. No. 3,554,966 and US Pat. No. 5,693,227.

In addition, the fluorinated ethers of aromatic acids are strong polys with slow heating from above 100 ° C. up to about 180 ° C. under reduced pressure, as disclosed in US Pat. No. 5,674,969 (inclusive as part of the present invention for all purposes). Condensation polymerization in phosphoric acid, followed by precipitation in water to polymerize with trihydrochloride-1 hydrate of tetraaminopyridine; Or about 50, as disclosed in US Provisional Patent Application No. 60 / 665,737, filed March 28, 2005, published as International Patent Publication WO 2006/104974, which is incorporated in its entirety for all purposes. The monomers can be mixed to form oligomers at a temperature of from about < RTI ID = 0.0 > Polymers that may be so produced are pyridobisimidazole-2,6-diyl (2,5-diaalkoxy-p-phenylene) polymers or pyridobisimidazole-2,6-diyl (2,5 -Diareneoxy-p-phenylene) polymers, for example poly (l, 4- (2,5-diareneoxy) phenylene-2,6-pyrido [2, 3-d: 5,6 -d '] bisimidazole) polymer. However, the pyridobisimidazole portion thereof may be replaced with any one or more of benzobisimidazole, benzobisthiazole, benzobisoxazole, pyridobisthiazole and pyridobisoxazole; Its 2,5-diaalkoxy-p-phenylene moiety isophthalic acid, terephthalic acid, 2,5-pyridine dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4-diphenyl dicarboxylic acid, One or more alkyl or aryl ethers of 2,6-quinoline dicarboxylic acid, and 2,6-bis (4-carboxyphenyl) pyridobisimidazole, and such fluorinated ethers are disclosed herein. It is generated according to the method.

Polymers made in such a way may, for example, comprise one or more of the following units:

Pyridobisimidazole-2,6-diyl (2,5-dialkoxy-p-phenylene) and / or pyridobisimidazole-2,6-diyl (2,5-diphenoxy-p -Phenylene) units;

Pyridobisimidazole-2,6-diyl (2,5-dimethoxy-p-phenylene), pyridobisimidazole-2,6-diyl (2,5-diethoxy-p- Phenylene), pyridobisimidazole-2,6-diyl (2,5-dipropoxy-p-phenylene), pyridobisimidazole-2,6-diyl (2,5-dibu Oxy-p-phenylene) and pyridobisimidazole-2,6-diyl (2,5-diphenoxy-p-phenylene);

Pyridobisthiazole-2,6-diyl (2,5-dialkoxy-p-phenylene) and / or pyridobisthiazole-2,6-diyl (2,5-diphenoxy-p-phenyl Ren) units;

Pyridobisthiazole-2,6-diyl (2,5-dimethoxy-p-phenylene), pyridobisthiazole-2,6-diyl (2,5-diethoxy-p-phenylene ), Pyridobisthiazole-2,6-diyl (2,5-dipropoxy-p-phenylene), pyridobisthiazole-2,6-diyl (2,5-dibutoxy-p- Phenylene) and pyridobisthiazole-2,6-diyl (2,5-diphenoxy-p-phenylene);

Pyridobisoxazole-2,6-diyl (2,5-dialkoxy-p-phenylene) and / or pyridobisoxazole-2,6-diyl (2,5-diphenoxy-p -Phenylene) units;

Pyridobisoxazole-2,6-diyl (2,5-dimethoxy-p-phenylene), pyridobisoxazole-2,6-diyl (2,5-diethoxy-p- Phenylene), pyridobisoxazole-2,6-diyl (2,5-dipropoxy-p-phenylene), pyridobisoxazole-2,6-diyl (2,5-dibu Oxy-p-phenylene) and pyridobisoxazole-2,6-diyl (2,5-diphenoxy-p-phenylene);

Benzobisimidazole-2,6-diyl (2,5-dialkoxy-p-phenylene) and / or benzobisimidazole-2,6-diyl (2,5-diphenoxy-p-phenyl Ren) units;

Benzobisimidazole-2,6-diyl (2,5-dimethoxy-p-phenylene), benzobisimidazole-2,6-diyl (2,5-diethoxy-p-phenylene ), Benzobisimidazole-2,6-diyl (2,5-dipropoxy-p-phenylene), benzobisimidazole-2,6-diyl (2,5-dibutoxy-p- Phenylene) and benzobisimidazole-2,6-diyl (2,5-diphenoxy-p-phenylene);

Benzobisthiazole-2,6-diyl (2,5-dialkoxy-p-phenylene) and / or benzobisthiazole-2,6-diyl (2,5-diphenoxy-p-phenylene) unit;

Benzobisthiazole-2,6-diyl (2,5-dimethoxy-p-phenylene), benzobisthiazole-2,6-diyl (2,5-diethoxy-p-phenylene), Benzobisthiazole-2,6-diyl (2,5-dipropoxy-p-phenylene), benzobisthiazole-2,6-diyl (2,5-dibutoxy-p-phenylene) and A unit selected from the group consisting of benzobisthiazole-2,6-diyl (2,5-diphenoxy-p-phenylene);

Benzobisoxazole-2,6-diyl (2,5-dialkoxy-p-phenylene) and / or benzobisoxazole-2,6-diyl (2,5-diphenoxy-p-phenyl Ren) units; And / or

Benzobisoxazole-2,6-diyl (2,5-dimethoxy-p-phenylene), benzobisoxazole-2,6-diyl (2,5-diethoxy-p-phenylene ), Benzobisoxazole-2,6-diyl (2,5-dipropoxy-p-phenylene), benzobisoxazole-2,6-diyl (2,5-dibutoxy-p- Phenylene) and benzobisoxazole-2,6-diyl (2,5-diphenoxy-p-phenylene).

Example

Advantageous properties and effects of the process of the invention can be seen in the laboratory examples as described below. The embodiments of this method on which the examples are based are merely representative, and the choice of such embodiments to illustrate the invention is contemplated by conditions, arrangements, approaches, steps, techniques, configurations or reactants not described in the examples. It is not intended that the subject matter, which is not suitable for carrying out or which is not described in the examples, be excluded from the scope of the appended claims and their equivalents.

The meaning of the abbreviations is as follows: "mL" means milliliters, "g" means grams, "mmol" means millimoles, "N" means normal, "THF" means tetrahydro Means furan.

Example  1.2,5-bis (2,2,2- Trifluoroethoxy Preparation of Terephthalic Acid

To the solution of 8 mL 2,2,2-trifluoroethanol (CF ₃ CH ₂ OH) in 15 mL of THF is carefully added 0.19 g (7.9 mmol) of sodium hydride. When gas evolution is complete, 0.488 g (1.5 mmol) of 2,5-dibromoterephthalic acid is added to the solution, followed by CuBr ₂ (0.092 mmol) and 2,2 ', 6, in 1.5 mL of CF ₃ CH ₂ OH. A solution of 6'-tetramethylheptanedionone-3,5 (0.19 mmol) is added. The resulting pale blue slurry is heated at 60 ° C. for 4 days. HCl aqueous solution (1 N) is added to precipitate the product. The product is washed with water, then dissolved in methanol and the resulting solution is filtered. Methanol is removed under vacuum to afford product 2,5-bis (2,2,2-trifluoroethoxy) terephthalic acid as colorless microcrystals.

Example 2. Preparation of 2,5-bis (2,2,3,3-tetrafluoropropoxy) terephthalic acid

The flask is filled with 5 mL of dry THF and 8.1 mmol of sodium hydride. A solution of 1.5 g (11.4 mmol) of 2,2,3,3-tetrafluoropropanol (HCF ₂ CF ₂ CH ₂ OH) in 5 mL of THF is added dropwise. When gas evolution is complete, 2,5-dibromoterephthalic acid (1.51 mmol) is added to the colorless solution. Next, a mixture of CuBr ₂ (0.13 mmol) and 2,4-pentanedione (0.22 mmol) in 0.5 g HCF ₂ CF ₂ CH ₂ OH is added to the solution. The resulting pale blue slurry is heated at 60 ° C. for 2 days. The cooled reaction product is treated with 0.5 N HCl, then with water and the precipitate is washed with water to isolate the product 2,5-bis (2,2,3,3-tetrafluoropropoxy) terephthalic acid.

Each formula shown herein selects (1) one variable radical, substituent, or numerical coefficient from within the defined range, while all other variable radicals, substituents, or numerical coefficients remain constant, and (2) each With respect to the remaining variable radicals, substituents, or numerical coefficients of, each and all of the separate individual compounds that can be formed in such formulas are described by sequentially making the same selection from within the defined range, with the remainder being constant. In addition to the choices made for any variable radical, substituent, or numerical coefficient of only one of the members of the group described by said range within the defined range, more than one of the entire group of radicals, substituents, or numerical coefficients, A plurality of compounds can be described by selecting fewer members. The selection made within the ranges defined for any variable radical, substituent or numerical coefficient comprises (i) only one of the members of the entire group described by said range, or (ii) one of the members of the entire group. When a subgroup includes more than but less than all members, the selected member (s) are selected by excluding the member (s) of the entire group that are not selected to form the subgroup. Such compounds or a plurality of compounds may in that case be characterized by the definition of one or more variable radicals, substituents or numerical coefficients, which definitions refer to the entire group of defined ranges for such variables but are not used to form subgroups. The excluded member (s) do not exist in the entire group.

When a range of numerical values is mentioned in the present invention, the range includes the endpoint and all individual integers and fractions within that range, and also those endpoints for forming a subgroup of a larger group of values within the stated range and Each of the narrower ranges formed therein by all possible various combinations of internal integers and fractions includes the same extent as if each of these narrower ranges were explicitly mentioned. When a range of numerical values is described herein as being above the stated values, the ranges are nevertheless finite, and the ranges are defined at their upper limits by values operable within the context of the invention described herein. Boundaries are made. When a range of numerical values is described herein as being less than the stated value, the range is nevertheless bounded by a nonzero value at the lower end of the range.

In this specification, unless expressly stated otherwise or contrary to the usage relationship, the amounts, sizes, ranges, and other quantities and features mentioned herein need not be accurate, especially when modified by the term “about”, The inclusion of tolerances, conversion factors, rounding, measurement errors, etc., and other values within the stated value that have a functional equivalent and / or operable equivalent to the values described within the context of the present invention. May be approximate and / or larger or smaller (as desired) than described.

When an embodiment of the present invention is described or described as including, containing, containing, containing, having, consisting of, or consisting of certain features, such art or description is not expressly provided to the contrary, unless such description or description is clearly provided to the contrary. It should be understood that one or more features in addition to the described or described features may be present in the embodiments. However, alternative embodiments of the present invention may be described or described as consisting essentially of certain features, in which no feature exists in the embodiment that significantly changes the operating principle or distinctive features of the embodiment. . Further alternative embodiments of the present invention may be described or described as consisting of certain features, in which only features are specifically described or described.

Claims (15)

Formula I:
(I)

Wherein Ar is a C ₆ to C ₂₀ monocyclic or polycyclic aromatic nucleus, n and m are each independently a non-zero value, n + m is 8 or less, and R _f is optionally one or more Fluorinated alkyl, alkaryl, aralkyl, or aryl groups, including the ether linking group —O—, provided that R _f is attached to the ether oxygen of Formula (I) via a CF ₂ group or a CF ₂ CH ₂ CH ₂ group A process for producing a fluorinated ether of an aromatic acid, represented by the structure of
(a) Formula II:
[Formula II]

Halogenated aromatic acids represented by the structure of wherein each X is independently Cl, Br or I, and Ar, n and m are as described above,
(i) a total of about n + m to about n + m + 1 equivalents of alcoholate R _f O ^- M ^{+ in a} polar aprotic solvent or in R _f OH as a solvent, per equivalent of halogenated aromatic acid M is Na or K);
(ii) a copper (I) or copper (II) source; And
(iii) Formula III:
[Formula III]

(Where A is

,

,

, or

ego,
R ¹ and R ² are each independently substituted and unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl and tertiary alkyl groups; And substituted and unsubstituted C ₆ -C ₃₀ aryl and heteroaryl groups;
R ³ is H; Substituted and unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl and tertiary alkyl groups; Substituted and unsubstituted C ₆ -C ₃₀ aryl and heteroaryl groups; And halogen;
R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently H or a substituted or unsubstituted C ₁ -C ₁₆ n-alkyl, iso-alkyl or tertiary alkyl group; p is contacted with a diketone ligand coordinated to copper, as represented by the structure of 0 or 1,
Forming a reaction mixture;
(b) by heating the reaction mixture, the formula IV:
[Formula IV]

Forming an m-basic salt of the product of step (a), as represented by the structure of;
(c) optionally, separating the m-basic salt of formula IV from the reaction mixture in which the m-basic salt of formula IV is formed; And
(d) contacting the m-basic salt of formula IV with an acid to form a fluorinated ether of an aromatic acid therefrom. The compound of claim 1, wherein R _f is
CF ₃ (CF ₂ ) _a (CH ₂ ) _b −, where a is an integer from 0 to 15 and b is 1, 3 or 4;
HCF ₂ (CF ₂ ) _c (CH ₂ ) _d −, where c is an integer from 0 to 15 and d is 1, 3, or 4;
CF ₃ CF ₂ CF ₂ OCFHCF ₂ (OCH ₂ CH ₂ ) _e -and
CF ₃ CF ₂ CF ₂ OCF ₂ CF ₂ (OCH ₂ CH ₂ ) _e −, where e is an integer from 1 to 12;
(CF ₃ ) ₂ CH-,
(CF ₃ CF ₂ CFH) (F) (CF ₃ ) C-,
(CF ₃ CF ₂ CFH) (F) (CF ₃ ) CCH _2- , (CF ₃ ) ₂ (H) C (CF ₃ CF ₂ ) (F) C-, and
(CF ₃ ) ₂ (H) C (CF ₃ CF ₂ ) (F) CCH ₂ —; And
Pentafluorophenyl. The halogenated aromatic acid of claim 1, wherein the halogenated aromatic acid is 2-bromobenzoic acid, 2,5-dibromobenzoic acid, 2-bromo-5-nitrobenzoic acid, 2-bromo-5-methylbenzoic acid, 2-chlorobenzoic acid, 2 , 5-dichlorobenzoic acid, 2-chloro-3,5-dinitrobenzoic acid, 2-chloro-5-methylbenzoic acid, 2-bromo-5-methoxybenzoic acid, 5-bromo-2-chlorobenzoic acid, 2 With, 3-dichlorobenzoic acid, 2-chloro-4-nitrobenzoic acid, 2,5-dichloroterephthalic acid, 2-chloro-5-nitrobenzoic acid, 2,5-dibromoterephthalic acid, and 2,5-dichloroterephthalic acid The method is selected from the group consisting of. 2. The process of claim 1, wherein in step (a), a normal equivalent of R _f O ⁻ M ⁺ is added to the reaction mixture in a total of about n + m to n + m + 1 per equivalent of halogenated aromatic acid. The method of claim 1, wherein the copper source comprises a Cu (I) salt, a Cu (II) salt, or a mixture thereof. The copper source of claim 5 wherein the copper source is selected from the group consisting of CuCl, CuBr, CuI, Cu ₂ SO ₄ , CuNO ₃ , CuCl ₂ , CuBr ₂ , CuI ₂ , CuSO ₄ , Cu (NO ₃ ) ₂ , and mixtures thereof. How to be. The method of claim 1, wherein the ligand is 2,4-pentanedione, 2,3-pentanedione or 2,2 ', 6,6'-tetramethylheptanedionone-3,5 (Formula V):
(V)

The method of claim 1, further comprising combining the copper source and the ligand prior to adding the copper source and the ligand to the reaction mixture. The method of claim 6, wherein the copper source comprises CuBr or CuBr ₂ . The method of claim 1, wherein the copper is provided in an amount of about 0.1 to about 5 mol%, based on the moles of halogenated aromatic acid. The method of claim 1, wherein the ligand is provided in an amount of about 1 to about 2 molar equivalents per mole of copper. The compound of claim 1, wherein the halogenated aromatic hydroxy acid comprises 2,5-dibromoterephthalic acid or 2,5-dichloroterephthalic acid; The copper source comprises CuBr, CuBr ₂ or a mixture of CuBr and CuBr ₂ ; The copper source is provided in an amount of about 0.1 to about 5 mol% based on the moles of halogenated aromatic acid; The ligand is 2,4-pentanedione, 2,3-pentanedione or 2,2 ', 6,6'-tetramethylheptanedionone-3,5; The ligand is provided in an amount of about 1 to about 2 molar equivalents per mole of copper. The method of claim 1, further comprising reacting the ether of the aromatic acid to produce a compound, monomer, oligomer, or polymer therefrom. The polymer of claim 13 wherein the polymer produced is at least one member of the group consisting of pyridobisimidazole, pyridobisthiazole, pyridobisoxazole, benzobisimidazole, benzobisthiazole, and benzobisoxazole moiety. How to include. 15. The polymer of claim 14 wherein the polymer produced is a fluorinated pyridobisimidazole-2,6-diyl (2,5-dialkoxy-p-phenylene) polymer or a fluorinated pyridobisimidazole-2 , 6-diyl (2,5-diareneoxy-p-phenylene) polymer.